BRPI0517080B1 - wastewater treatment device by anodic oxidation and wastewater treatment process. - Google Patents

wastewater treatment device by anodic oxidation and wastewater treatment process. Download PDF

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Publication number
BRPI0517080B1
BRPI0517080B1 BRPI0517080A BRPI0517080A BRPI0517080B1 BR PI0517080 B1 BRPI0517080 B1 BR PI0517080B1 BR PI0517080 A BRPI0517080 A BR PI0517080A BR PI0517080 A BRPI0517080 A BR PI0517080A BR PI0517080 B1 BRPI0517080 B1 BR PI0517080B1
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BR
Brazil
Prior art keywords
anode
electrolyser
type
wastewater treatment
oxygen evolution
Prior art date
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BRPI0517080A
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Portuguese (pt)
Inventor
Didier Carle Gaston Grange
Paolo Rossi
Yves Lucien Pellet
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Industrie De Nora Spa
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Publication date
Application filed by Industrie De Nora Spa filed Critical Industrie De Nora Spa
Publication of BRPI0517080A publication Critical patent/BRPI0517080A/en
Publication of BRPI0517080B1 publication Critical patent/BRPI0517080B1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46147—Diamond coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4614—Current
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]

Abstract

The invention relates to an effluent COD treatment procedure by anodic oxidation combining the use of two different types of anode with a suitable apportionment of current. The first type of anode comprises an anode based on diamond doped-synthetic diamond. The second type of anode comprises an anode with high oxygen overvoltage containing tin and antimony oxides.

Description

Relatório Descritivo da Patente de Invenção para "DISPOSITIVO DE TRATAMENTO DE DQO DE EFLUENTES ATRAVÉS DE OXIDAÇÃO ANÓDICA E PROCESSO DE TRATAMENTO DE DQO DE EFLUENTES".Report of the Invention Patent for "Effluent Cd Treatment Device through Anode Oxidation and Effluent Cd Treatment Process".

Os efluentes muito ricos de DQO (Demanda Química de Oxigênio) comportam alguns problemas no momento em que os mesmos devam ser tratados antes do seu envio para a estação de purificação biológica. Por esse motivo foram estudadas técnicas eletroquímicas de pré-tratamento de DQO. A oxidação de DQO pode ser efetuada mediante eletrólise em ânodos caracterizados por uma forte tensão excedente da reação de evolução de oxigênio ou com propriedades eletrocatalíticas específicas.Very rich COD (Chemical Oxygen Demand) effluents cause some problems when they must be treated before they are sent to the biological purification station. For this reason, electrochemical COD pretreatment techniques were studied. COD oxidation can be performed by electrolysis at anodes characterized by a strong excess voltage of the oxygen evolution reaction or with specific electrocatalytic properties.

Os elétrodos revestidos com óxidos de estanho e antimônio são incluídos nessa tipologia, e serão utilizados a seguir como exemplo não limi-tante de ânodos à elevada tensão excedente de oxigênio. Tais elétrodos foram utilizados em eletrolisadores simples conhecidos na técnica, por exemplo em eletrolisadores do tipo fluxo perpendicular. Em tais eletrolisadores a solução a ser tratada passa alternativamente através dos ânodos e cátodos, que se apresentam sob a forma de redes ou esponjas. Foi efetivamente observada uma redução de DQO de certos efluentes através dessa técnica, não obstante um rendimento farádico muito baixo é associado a tal sistema, mesmo que a redução de DQO seja tão baixa quanto aproximadamente 50%.Tin and antimony oxide-coated electrodes are included in this typology, and will be used below as a non-limiting example of anodes to the high excess oxygen tension. Such electrodes have been used in simple electrolysers known in the art, for example in perpendicular flow type electrolysers. In such electrolysers the solution to be treated alternatively passes through the anodes and cathodes, which are in the form of nets or sponges. A COD reduction of certain effluents was effectively observed by this technique, although a very low tidal yield is associated with such a system, even though the COD reduction is as low as approximately 50%.

Existe um outro tipo de elétrodo que há uma maior tensão excedente de oxigênio em relação aos ânodos com óxidos de estanho e de antimônio, ou seja, o elétrodo de diamante dopado com boro (BDD), que é constituído por uma camada de diamante dopado com boro depositado sobre um suporte condutivo. Os inconvenientes apresentados por este elétrodo são de dois tipos, em outras palavras o seu custo e a relativa fragilidade que requerem a utilização de eletrolisadores especiais de custo elevado; por outro lado, graças ao valor de potencial de reação suficientemente mais elevado, isso conduz a obtenção das taxas de redução de DQO muito maiores com melhores rendimentos farádicos. Pode-se supôr que, devido ao elevado potencial de reação, um número de moléculas que irão constituir o DQO sejam degradadas através da dissociação de suas correntes. A invenção consiste na utilização simultânea em série ou em paralelo de ao menos dois tipos de elétrodo. O princípio é utilizar em máximo grau os elementos mais práticos e menos onerosos, ou seja os ânodos à base de óxidos de estanho e antimônio ou outros elétrodos equivalentes, em um reator eletroquímico convencional a lâmina ou tubo, e posteriormente de utilizar o elétrodo BBD com o seu próprio catalisador para efetuar a parte da reação que não pode ser realizada nos ânodos à base de óxido de estanho e antimônio ou nos seus equivalentes. Sendo as moléculas que constituem o DQO parcialmente degradadas graças ao ânodo BDD, torna-se mais fácil prosseguir a sua oxidação no ânodo à base de óxidos de estanho e de antimônio, como confirmado pelas observações experimentais. Para cada tipo de efluente ocorrerá determinar a divisão proporcional mais conveniente da corrente elétrica para os dois processos de oxidação no BDD e no elétrodo à base de óxidos de estanho e antimônio. A divisão proporcional de corrente ideal é geralmente compreendida entre 55:45 e 95:5, dependendo do tipo de efluente; tal divisão proporcional pode ser obtida de maneira muito simples agindo na superfície anódica geral de cada eletrolisador (por exemplo fixando a razão entre superfície anódica geral do ânodo à base de óxidos de estanho e antimônio com respeito ao BDD a um valor compreendido entre 55:45 e 95:5), mas outras soluções também são possíveis. Para instalações que devam tratar de diversos tipos de efluentes, é oportuno que tal divisão proporcional de corrente possa ser regulada de acordo com sistemas conhecidos. O elétrodo à base de óxido de estanho e antimônio pode ser construído de acordo com várias tipologias, por exemplo pode ser um elétrodo cerâmico, por exemplo sinterizado pelos pós de dois óxidos eventualmente misturados a outros componentes, ou pode ser constituído por uma base metálica, por exemplo de titânio ou outro metal de válvula, revestida com os óxidos de estanho e antimônio eventualmente misturados em pequenas quantidades de elementos condutivos (por exemplo cobre) ou com desejáveis propriedades eletrocatalíticas (por exemplo irídio) a fim de ajustar seu potencial. A princípio, puderam-se utilizar também ânodos de titânio revestido com eletrocatalisadores para evolução de oxigênio (por exemplo misturas de óxidos de irídio e tantálio), todavia as tensões excedentes de oxigênio neste caso resultam muito baixas e os resultados obtidos mediante o acoplamento de eletrolisadores da invenção resultam menos favoráveis. São relatados a seguir, os resultados relativos ao tratamento de DQO de um típico banho de desengraxamento. Com elétrodos revestidos com óxidos de estanho e antimônio, utilizados em um eletrolisador tipo RE-TEC®, no decorrer de 100 horas a DQO diminuiu pela metade com um rendimento farádico médio de aproximadamente 7%. Uma vez acoplado o precedente eletrolisador com um segundo eletrolisador contendo o elétrodo BDD, impostando 90% da corrente no eletrolisador RETEC® e 10% no eletrolisador contendo o BDD, no decorrer de aproximadamente 100 horas alcançou-se a destruição de 80% da DQO com um rendimento farádico médio superior aos 24%.There is another type of electrode where there is a higher excess oxygen tension than the tin oxide and antimony anodes, ie the boron-doped diamond (BDD) electrode, which consists of a diamond-doped diamond layer. boron deposited on a conductive support. The disadvantages presented by this electrode are of two types, in other words its cost and relative fragility which require the use of special high cost electrolysers; On the other hand, thanks to the sufficiently higher reaction potential value, this leads to the achievement of much higher COD reduction rates with better faradic yields. It can be assumed that due to the high reaction potential, a number of molecules that will constitute the COD are degraded by dissociating their currents. The invention consists of simultaneous series or parallel use of at least two types of electrode. The principle is to use the most practical and least costly elements, ie tin and antimony oxide based anodes or other equivalent electrodes, in a conventional electrochemical ball or tube reactor, and then to use the BBD electrode with its own catalyst to effect the part of the reaction that cannot be performed on the tin oxide and antimony anodes or their equivalents. Since the molecules that make up the COD are partially degraded thanks to the BDD anode, it is easier to continue their oxidation at the anode based on tin oxides and antimony, as confirmed by experimental observations. For each type of effluent the most convenient proportional division of the electric current will be determined for the two oxidation processes in the BDD and the tin oxide-based antimony electrode. The proportional division of ideal current is generally between 55:45 and 95: 5, depending on the type of effluent; Such a proportional division can be achieved very simply by acting on the general anodic surface of each electrolyser (for example by setting the ratio of the general anode anode surface of tin oxide to antimony with respect to BDD at 55:45). and 95: 5), but other solutions are also possible. For installations dealing with various types of effluent, it is appropriate that such proportional current division can be regulated according to known systems. The tin oxide and antimony based electrode may be constructed according to various types, for example it may be a ceramic electrode, for example sintered by the two oxide powders possibly mixed with other components, or may consist of a metal base, for example titanium or other valve metal, coated with tin and antimony oxides possibly mixed in small amounts of conductive elements (eg copper) or with desirable electrocatalytic properties (eg iridium) to adjust their potential. At first, electrocatalyst-coated titanium anodes could be used for oxygen evolution (eg mixtures of iridium and tantalum oxides), but the excess oxygen stresses in this case are very low and the results obtained by coupling electrolysers. of the invention are less favorable. The following are the results related to the COD treatment of a typical degreasing bath. With tin and antimony oxide coated electrodes used in a RE-TEC® electrolyser, over 100 hours the COD has halved with an average tidal yield of approximately 7%. Once the preceding electrolyzer was coupled with a second electrolyzer containing the BDD electrode, imposing 90% of the current on the RETEC® electrolyzer and 10% on the BDD containing electrolyzer, the destruction of 80% of the COD was achieved within approximately 100 hours. an average farm yield greater than 24%.

Este método permite assim melhorar fortemente a taxa de DQO destruída, com um melhor rendimento farádico (menores custos de energia elétrica), e ao mesmo tempo limitando o investimento econômico derivante do uso de BDD restringindo a própria aplicação à um pequeno percentual do tratamento.This method thus allows to greatly improve the rate of destroyed COD, with a better faradic yield (lower electricity costs), while limiting the economic investment derived from the use of BDD by restricting the application itself to a small percentage of treatment.

Claims (7)

1. Dispositivo de tratamento de DQO de efluentes através de oxidação anódica, caracterizado por compreender um primeiro eletrolisador equipado com um primeiro tipo de ânodo para evolução de oxigênio conectado em série ou em paralelo ao menos a um segundo eletrolisador equipado com um segundo tipo de ânodo para evolução de oxigênio, em que o referido segundo tipo de ânodo é um ânodo de diamante dopado com boro e tem maior tensão excedente para evolução de oxigênio do que referido primeiro tipo de ânodo.1. Anode oxidation effluent COD treatment device, characterized in that it comprises a first electrolyser equipped with a first type of oxygen evolution anode connected in series or in parallel to at least a second electrolyser equipped with a second type of anode. for oxygen evolution, wherein said second anode type is a boron-doped diamond anode and has greater excess oxygen evolution voltage than said first anode type. 2. Dispositivo de acordo com a reivindicação 1, caracterizado pelo fato de que o referido segundo eletrolisador há uma superfície anódica inferior àquela do referido primeiro eletrolisador.Device according to claim 1, characterized in that said second electrolyser has an anodic surface less than that of said first electrolyser. 3. Dispositivo de acordo com as reivindicações 1 ou 2, caracterizado pelo fato de que o referido primeiro tipo de ânodo para evolução de oxigênio de referido primeiro eletrolisador compreende óxidos de estanho e antimônio.Device according to claim 1 or 2, characterized in that said first type of oxygen evolution anode of said first electrolyser comprises tin oxides and antimony. 4. Dispositivo de acordo com a reivindicação 2, caracterizado pelo fato de que a razão entre a superfície ativa de referido primeiro eletrolisador e a superfície ativa do referido segundo eletrolisador é compreendida entre 55:45 e 95:5.Device according to claim 2, characterized in that the ratio of the active surface of said first electrolyser to the active surface of said second electrolyser is between 55:45 and 95: 5. 5. Dispositivo de acordo com qualquer uma das reivindicações 1 a 4, caracterizado pelo fato de que a razão entre a corrente elétrica fornecida ao referido primeiro e ao referido segundo eletrolisador pode ser variada.Device according to any one of claims 1 to 4, characterized in that the ratio of the electric current supplied to said first and said second electrolyser may be varied. 6. Processo de tratamento de DQO de efluentes caracterizado por compreender a realização de um processo de oxidação anódica no dispositivo como definido em qualquer uma das reivindicações precedentes.Wastewater COD treatment process comprising an anodic oxidation process in the device as defined in any one of the preceding claims. 7. Processo de acordo com a reivindicação 6, caracterizado pelo fato de que a razão entre a corrente elétrica fornecida ao referido primeiro e ao referido segundo eletrolisador é compreendida entre 55:45 e 95:5.Process according to Claim 6, characterized in that the ratio of the electric current supplied to said first and said second electrolyser is between 55:45 and 95: 5.
BRPI0517080A 2004-10-18 2005-10-18 wastewater treatment device by anodic oxidation and wastewater treatment process. BRPI0517080B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT001974A ITMI20041974A1 (en) 2004-10-18 2004-10-18 IMPROVEMENT OF THE COD KILLING PROCESS FOR ELECTROCHEMICAL OXIDATION
PCT/EP2005/011197 WO2006042741A1 (en) 2004-10-18 2005-10-18 Improved cod abatement process for electrochemical oxidation

Publications (2)

Publication Number Publication Date
BRPI0517080A BRPI0517080A (en) 2008-09-30
BRPI0517080B1 true BRPI0517080B1 (en) 2016-04-26

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BRPI0517080A BRPI0517080B1 (en) 2004-10-18 2005-10-18 wastewater treatment device by anodic oxidation and wastewater treatment process.

Country Status (14)

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US (1) US10144659B2 (en)
EP (1) EP1807357B1 (en)
JP (1) JP4782793B2 (en)
KR (1) KR101214824B1 (en)
CN (1) CN101090870B (en)
AT (1) ATE535499T1 (en)
AU (1) AU2005296759B2 (en)
BR (1) BRPI0517080B1 (en)
ES (1) ES2378997T3 (en)
IT (1) ITMI20041974A1 (en)
MX (1) MX2007004562A (en)
RU (1) RU2393997C2 (en)
WO (1) WO2006042741A1 (en)
ZA (1) ZA200703511B (en)

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WO2011120702A1 (en) * 2010-03-31 2011-10-06 Aseca Ag Electrolysis cell and system and process for production of an electrochemically activated solution by electrolysis
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Also Published As

Publication number Publication date
CN101090870B (en) 2013-05-08
JP2008516762A (en) 2008-05-22
JP4782793B2 (en) 2011-09-28
RU2393997C2 (en) 2010-07-10
KR101214824B1 (en) 2012-12-24
ATE535499T1 (en) 2011-12-15
ES2378997T3 (en) 2012-04-19
MX2007004562A (en) 2007-08-14
WO2006042741A1 (en) 2006-04-27
EP1807357B1 (en) 2011-11-30
AU2005296759A1 (en) 2006-04-27
ITMI20041974A1 (en) 2005-01-18
US20080087552A1 (en) 2008-04-17
ZA200703511B (en) 2008-10-29
RU2007118489A (en) 2008-11-27
EP1807357A1 (en) 2007-07-18
KR20070083721A (en) 2007-08-24
CN101090870A (en) 2007-12-19
US10144659B2 (en) 2018-12-04
BRPI0517080A (en) 2008-09-30
AU2005296759B2 (en) 2010-02-25

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B07A Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]
B06A Patent application procedure suspended [chapter 6.1 patent gazette]
B09A Decision: intention to grant [chapter 9.1 patent gazette]
B16A Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]

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